Polyazo-dyestuffs



United rates 3,078,266 POLYAZG-DYESTUFFS Walter Hanhart, Riehen, Switzerland, assignor to Ciha Limited, Basel, Switzerland, a Swiss firm No Drawing. Filed July 20, 1959, Ser. No. 828,037 Claims priority, application Switzerland Aug. 6, 1958 8 Claims. (Cl. 260-446) This invention provides valuable new polyazo-dyestuifs of the general formula O O-NH CO-N in which R represents the radical of a (haze-component containing at least one azo linkage, and which radical contains in a position vicinal to the -N:N-A- grouping a group capable of taking part in the formation of heavy metal complexes, and A represents the radical of a hydroxynaphthalene sulfonic acid bound to the RN=N-- group in a position vicinal to the hydroxyl group, and also provides complex heavy metal compounds, especially complex copper compounds, of the poiyazodyestuif of the above formula.

The invention also provides a Process for the manufacture of the dyestuffs of the above general Formula 1, wherein barbituric acid is coupled With a diazo compound of an amino-polyazo-dyestuff of the general formula or of a complex heavy metal compound of such dye stuff, in which formula R represents the radical of a diam-component containing at least one azo linkage, and which radical contains in a position vicinal to the N=NA grouping a group capable of taking part in the formation of heavy metal complexes, and A represents the radical of a hydroxynaphthalene sulfonic acid bound to the azo linkage in a position vicinal to the hydroxyl group, and which radical advantageously contains the -NH group bound directly to the naphthalene nucleus.

The metal-free dyestuffs of the Formula 2 used as starting materials can be obtained by coupling an aminonaphthol sulfonic acid (for example, Z-amino-S-hydroxynaphthalene-7-sulfonic acid, Z-amino--hydroxynaphthalene-8-sulfonic acid, Z-amino-8-hydroxynaphthalene-G-sulfonic acid or 1-amino-8-hydroxynaphthalene-3:6- or -4:6- disulfonic acid) in a position vicinal to the hydroxyl group with a diazo-compound of an amino-azo-dyestuif of the formula RNH Which contains in a position vicinal to the diazo-group a grouping capable of taking part in the formation of metal complexes, for example, a carboxyl group or a hydroxyl group that may be etherified.

Instead of the aforesaid aminonaphthlo sulfonic acids, which contain the amino group bound directly to the naphthalene nucleus, there may be used aminonaphthol sulfonic acids which contain this diazotizable amino group in an external nucleus, for example, in a benzoyl radical. As examples of such aminonaphthol sulfonic acids there may be mentioned 2-(4'-aminophenylamino)-5-hydroxynaphthalene-7-sulfonic acid and more especially 2-(4'- aminobenzoylamino) 5 hydroxynaphthalene-7-sulfonic acid.

As diazotized amino-azo-dyestuffs there may be mentioned diam-compounds of amino-monoazoas well as amino-disazo-dyestuiis, which can be made by the usual methods, for example, by coupling any desired diazocompound with a coupling component containing a free amino group and containing in a position Vicinal to the 'free amino group a grouping capable of taking part in the formation ofmetal complexes,.for example, with a 2- Patented Feb. 19, 19%3 alkoxy-l-aminobenzene unsubstituted in the 4-position, such as Z-methoxy-l-aminobenzene, Z-methoxy-S-methyll-aminobenzene, 2:5-dimethoxyor 2:5-diethoxy-1-aminobenzene or the like, or with a 2-alkoxyor Z-carboxymethoxy-l-aminonaphthalene derivative, such as a 2- methoxy-l-amino-naphthalenc monosulfonic acid unsubstituted in the 4-position. As diazo-components to be coupled with such coupling components for making the starting components of the formula R-NH there may be mentioned:

(a) Simple benzene or naphthalene derivatives: aminosalicylic acid, aminobenzoic acids, aminobenzene-ortho-, -metaor -para-sulfonic acid, l-aminobenezene-Z:S-disulfonic acid, 4-chloro-l-aminobenzene-2-sulfonic acid, and also nitroor cholro-anilines, 4-amino-4-acetylaminodiphenyl-S-sulfonic acid, l-aminonaphthalene-S :o-disulfonic acid, 2-aminonaphthalene-4:S-disulfonic acid or dehydrothiotoluidine mon0- or di-sulfonic acids; (b) Amines containing azo linkages, such as amino-azobenzeue monoor di-sulfonic acid, and those obtainable by coupling a diazocompound of an amine mentioned under (a) with a cow pling component containing a diazotizable amino group, such as 3-methyl-aniline, 1-aminonaphtha1ene-6- or -7-sulfonic acid and also the coupling components mentioned above that contain amino groups, and also those obtainable by coupling a diazo-compound of a monoacylated diamine with any desired coupling component and subsequently hydrolyzing the acylamino group to form a .free amino group.

Useful amino-azo-dyest-uffs of the Formula 2 can be obtained by coupling a tetrazotized diamine, which contains in a position vicinal to the diazo-group a grouping capable of taking part in the formation of metal complexes, for example, by coupling tetrazotized 4:4'-di amino-3:3'-dimethoxy-diphenyl, on the one hand, with an aminonaphthol sulfonic acid capable of coupling in a position vicinal to the hydroxyl group and, on the other, With any desired coupling component, and advantageously one capable of forming metal complexes.

As diazo-components to be coupled with the aforesaid coupling components for making the starting compounds of the formula R-NH there may also be used the complex metal compounds thereof which are obtainable by the metallization of monoazodyestufr's obtainable, for example, from 1-aminophenyl-3-methyl-5-pyrazolones, 1- aminophenyl-3-carboxy-5-pyrazolones, l-aminostilbenyl- B-methyl-S-pyrazolone-Z:2"-disulfonic acid and diazotized ortho-arninophenols and sulfonic acids thereof or diazotized ortho-aminobenzoic acids and sulfonic acids thereof.

The dyestuffs of the Formula 2 can be made by the usual known methods. The initial components are advantageously coupled with the aminonaphthol sulfonic acids in an alkaline medium. Before or preferably after the diazotization and coupling of the amino-azo-dyestuffs so obtained, of which a large number is known with barbituric acid, they may be converted into complex metal compounds thereof. As agents yielding metal there may be used, for example, agents yielding nickel but preferably agents yielding copper. The treatment with the agent yielding metal is advantageously carried out in such manner that a complex metal compound of an ortho-carboxy-ortho'-hydroxyor ortho ortho dihydroxyazo-dyestuff is formed, that is to say, in such manner that any alkoxy group present in ortho-position to the axe linkage is split up and one atom of metal is bound in complex union, for example, with one ortho:ortho'-dihydroxy-azo-grouping or one ortho-hydroxy-ortho'-carboxyazo-grouping.

The treatment with the agent yielding metal is therefore to be carried out in such manner that an ortho:ortho'- Ii,d78,2%

dihydroxy-azo-copper complex is formed, when the metallizable grouping is an ortho:ortho'-dihydroxy-azoor orthohydroxy-ortho-alkoxy-azo-grouping. As is known this reaction takes place more easily with an ortho:orthodihydroxy-azo-grouping than with an ortho-hydroxyortho-alkoxy-azo-grouping, so that in the latter case a longer period of reaction and/ or a higher temperature is required. The metallization is carried out, for example, with a salt of divalent copper or nickel in a weakly acid aqueous medium. The dyestuffs can also be metallized by the known method in which the metallization is carried out in an aqueous medium advantageously for several hours in the vicinity of 100 C. with the use of a nickelor copper-tetrammine complex in the presence or absence of an excess of amine or ammonia. Of special advantage in some of these cases is the process of Patent No. 2,536,957, which is carried out in the presence of a hydroxyalkylamine, especially ethanolamine, or a copper complex derived therefrom.

The dyestuffs of the general Formula 2 which contain in a position vicinal to the azo linkage connecting R with A an alkoxy group bound to a naphthalene radical, for example, dyestuffs of which the radical R in the Formula 2 has the formula OCH:

in which R represents the radical of any desired diazocomponent, are in general advantageously coppered with copper sulfate in the presence of an alkali metal acetate.

On the other hand, those dyestulfs which contain at the aforesaid position in the molecule an alkoxybenzene radical, for example, a radical of the formula are advantageously converted into the ortho:ortho-dihydroxy-copper complex by means of a copper-tetrammine sulfate.

The metalliferous dyestuffs so obtained are also largely known and correspond to the Formula 2.

The diazo-compounds obtained from the amino-azodyestuffs of the Formula 2 or their complex metal compounds are coupled with barbituric acid to form the dyestufis of the Formula 1 advantageously in a weakly alkaline medium. The dyestuffs so obtained, which contain no heavy metal in complex union, can be metallized, for example, by the methods described above for metallizing the starting dyestuffs of the Formula 2.

The dyestnfis of this invention, that have the Formula 1, can also be made by a modification of the process described above, wherein a diazotized amino-azo-dyestuff, which contains in a position vicinal to the diazo group a grouping capable of taking part in the formation of metal complexes, for example, a hydroxyl, alkoxy or carboxyl group, is coupled with a monoazo-dyestuff of the formula o O-NH x-N=N-o o o o O-N in which X represents the radicalof a hydroxynaphthalene sulfonic acid capable of coupling in a position vicinal to the hydroxyl group and bound directly to the azo linkage, and, if desired, the polyazo-dyestutfs so obtained is converted into a complex heavy metal compound thereof.

For making the dyestuffs of the Formula 4 there may be used as diazo-components the amino naphthol sulfonic acids mentioned above for use as coupling components in making the dyestuffs of the Formula 2. As amino-azo-dyestutfs to be coupled with the dyestuffs of the Formula 4 there are used in this modification of the process the products obtainable by the methods described above for making the compounds of the formula R-NHg- The polyazo-dyestutfs of this invention are suitable for dyeing or printing a very wide variety of materials, for example, those of animal origin, such as Wool, silk or leather, and especially for dyeing or printing cellulosic materials, such as cotton, linen, artificial silk or staple fibers of regenerated cellulose. Those dyestuffs that contain no heavy metal or contain a metallizable group may be treated on the fiber or in the dyebath with an agent yielding a heavy metal, advantageously an agent yielding copper.

In some cases especially valuable dyeings are obtained by using the process in which a dyeing or print produced with the metal-free dyestufi is after-treated with an aqueous solution which contains a water-soluble, and especially complex, copper compound and a basic formaldehyde condensation product of a compound containing at least once an atomic grouping of the formula for example, dicyandiamide or dicyandiamidine, or a compound, for example, cyanamide, that is easily convertible into a compound containing such an atomic grouping. Such a process is described, for example, in Patent No. 2,526,106.

The dyeings produced with the new dyestuffs in the manner described above are usually distinguished by their good properties of wet fastness, and especially their very good fastness to light and good capacity for being discharged.

The following examples illustrate the invention, the parts and percentages being by weight:

Example 1 6.2 parts of the disazo-dyestutf of the formula OCH; m QN=N- N=N- H H0 8 NH:

are dissolved in parts of warm water in the form of the sodium salt. The solution is cooled to 5-10 C., 0.7 part of sodium nitrite is added dissolved in water, and

then 4 parts of hydrochloric acid of 30% strength are -is dried, and is a green-black powder which dissolves in water with a green coloration, and yields green dyeings on cotton or viscose.

Similar dyestuffs are obtained by using, instead of the dyestufi obtained from 1-amino-3-methylbenzene, one of the dyestuffs of the formulae given in column I of the following table, in which are given in columnlI the tints cupriferous barbituric acid-dyestuff.

of the dyeings produced on cotton with the finished I II S 03H 0 CH3 IiIO 1 C1-- -N=N N= Blziish green.

HO: S NHz S 0 3H (1) C H: H O

2 N==N N=N DO.

I H O 3 3 NH:

1 g 03H S 0 H 03H 0 OH: OH 3 HaC-N=N N=N Do.

H 03 S NH:

, H O: s v

S|02H 0 CH3 HO 4 HzCGOHN-C N=N N=N Do.

H 03s -NHz N O CHa HO 5 1 Green.

C N=N- -N=N H30 S SOSH HOaS NH:

I I H 025 S10 3H 0 CH3 H O o C N=N -N=H D0.

HOaS NHC OONH2 O CH; H 0

-N=N -N=N 7 v G Biuish green.

HOaS NH:

(i') 6H3 HO 8 -N=N N==N Do.

8 OzNHz H035 NH2 8 OaH O OH; HO

9 Cl-N=N Do.

HOaS m are dissolved in the form of the sodium salt in 75 parts of warm water. The solution is cooled to 10 C., 0.7 part of sodium nitrite, dissolved in water, is added, and then 4 parts of hydrochloric acid of 30% strength, diluted (IIOOH coon TABLE-Continued I II C| CHa H0 10 01330 OHNON=N -N=N Do.

H038 -NH: HOa S E; H0 11 O:NC -N=N N: Green.

H038 -NH: H035 H0315 OCH: H0 12 COHNC N=N N=N Bluish green.

Hoes --NH:

' Hols OCH: H0

13 041:: N=N Do.

S OsH HOaS NH2 dOzH 01 Example 2 with a little water, are added, and the whole is stirred in the cold for a few hours. Coupling is then carried out Parts of the dlsazo'dyestufi of the formula with 1.3 parts of barbituric acid in a solution rendered alkaline with sodium carbonate. When the coupling is 0 0H OCH HO o finished the preclpitated trisazo-dyestuff 1s filtered off, and H0 N: N=N 40 converted in acetic acid solution into its complex copper compound by heating it with copper acetate in known HOE NHa manner. When dry, the copper complex compound is a green-black powder which dissolves in water with a green H018 coloration, and yields green dyeings on cotton or viscose, which are fast to washing when after-treated with copper salts.

Similar dyestuffs are obtained by using, instead of the starting dyestutt of the above formula, the following disazo-dyestuffs.

OCH:

hour

OCH! HO NHC oQ-Nm son:

OCH: H0

Example 3 9 parts of the disazodyestufi' of the formula 611-" moo OOH;

H 8 SOaH are dissolved in the form of the sodium salt in 450 parts of hot water. The solution is then cooled with ice to about C., 0.7 part of sodium nitrite, dissolved in a small amount of water, is added, and diazotization is brought about by adding 5 parts of hydrochloric acid of strength. The whole is stirred for a few hours, while cooling, and then coupling is carried out with 1.3 parts of barbituric acid in a solution rendered alkaline with sodium carbonate. When the coupling is complete the trisazo-dycstufi formed is precipitated by the addition of sodium chloride, the dyestuff is filtered oif and and 1108s on moo 00H,

Example 4 7.9 parts of the trisazo-dyestuff of the formula SOaH OOH;

HO3|S on 113m o'orn H0 H0 s- NE:

Hogs I i are dissolved in the form of the sodium-salt in parts of hot water-and cooled by the addition of ice to 5-10 C. 0.7 part of sodium nitrite in aqueous solution and 4.5 parts of hydrochloric acid of 30% strength diluted with a little water are added, and the whole is stirred for a few hours in the cold. Coupling with 1.3 parts of barbituric acid is then carried out in a solution rendered alkaline with sodiumcarbonate. When the coupling is finished the precipitated dyestulf is filtered off, and converted into its complex copper compound in known manner by heating it with an ammoniacal solution of copper oxide. The complex copper compound, when dry, is a blackish powder which dissolves in water with a green coloration, and dyes cotton blackish olive-grey tints.

Similar dyestuffs are obtained by using as starting materials the following dyestuffs:

(I) C H3 H 0 N=N Blackish oliveegreen.

H O a S -NH:

Olive-green.

' I l v $11, Hols ---NH:

1 1 TABLE--Continued 1 2 can; H0 4 -N=N N=N N=N V Greyish olive.

soar: 1" 1103 s Nlit; 7

403E B0311 e031; 033 no a N=NON=N -N=N Green. T on! a 1103s NHi SOaH 03H slom mm 110 7 -N=N -N=N- N=1. Blucklsh olive-green.

HOaS NH:

otn s om s 091 0 OH: H0

s 01H s 031! s OaH OCH: (|)H 9.--..- H018 :N -N=N- N=N Green.

Ha H018 NH:

HOaS s 03H 8 0:11 0 OH: H0

10..... N= QN=N N=N Do H; HOzS NH: I

OH 03H H0=s (IJCHa H0 11- =N-N=N N: Do Hols H CH: HOsS- NH;

In the case of dyestuffs derived from l-amino-Z-mewith the monoazo-dyestufi of the formula thoxynaphthalene sulfonioacids from the coppering is advantageously carried out in an acetic acidmedjum.

The sequence of the operations can generally be varied, HO

for example, dyestufi No. 1 in the table can equally well be prepared by coupling the disaz o-dyestufi of the for- 1 mula (JO-NH v i V or by carrying out the copperingbefore the final coupling B0111 75 operation with barbituric acid.

' I3 Example 5 12.2 parts of the disazo-dyestuif of the formula t4 disulfonic acid, 1-aminonaphthalene-4-sulfonic acid or 2- aminonaphthalene-6-su1fonic acid.

OCH: OH

$03K are dissolved as the sodium salt in 120 parts of water. Example 6 At 54.6, an aqueous Solution Part of sodium 12.3 parts of the trisazo-dyestuif of the formula COOH . 1 Y HOgSON=N-O nitrite and 3.5 of hydrochloric acid of 30% strength,

Similar dyestufis are obtained by using instead of 1- aminonaphthalenel: 8-disu1fonic acid to form the triazole,

are dissolved as the sodium salt in 180 parts of warm a little water, are added. The whole is stirred for a few hours, while cooling, and coupling with 1.3 parts of barbituric acid is then carried out in a solution rendered alkaline with sodium carbonate. The precipitated dyestuff is filtered off, and converted into its complex copper compound by heating it in acetic acid solution with copper acetate. The complex copper compound, when dry, is a dark green powder which dissolves in water with a green coloration and yields olive-green dyeings on cotton.

Similar dyestuffs, which dye vegetable fibers green tints, are obtained by using trisazo-dyestufis of the formulae COOH 00-N-O I can: I l

c l o CH3 on Y coon I o ON N='N N=N -N=N-o HOaS- -NH2 O=N SOQH l H2 SOaH another aminonaphthalene sulfonic acid, such as l-amino- Example 7 naphthalene-3zd-disulfonic acid, 2-aminonaphtha1ene-5z7- 116 parts of ma trisazwdyesmfi of the formula SOQH C0011 OOH; H

in which n and m each is a positive whole number up to 2, m+n is at most 3, A is a radical selected from the are dissolved as the sodium salt in 200 parts of water. 0.7 part of sodium nitrite and 4 parts of hydrochloric acid of 30% strength, diluted with a little water, are added, group consisting of and the whole is stirred in the cold for a few hours on Coupling with 1.3 parts of bartituric acid is then carried 5 out in a solution rendered alkaline with sodium carbonate,

and the dyestuff formed is precipitated by adding parts p of sodium chloride for every 100 parts by volume of liq- H035 uor. By heating the precipitate in a weekly acetic acid solution with copper acetate the complex copper com- 10 pound is prepared in known manner. When dry it is a dark green powder which dissolves in water with a green 0H coloration and yields green dyeings on cotton or viscose.

Example 8 1.84 parts of 4:4'-diaminodipheny1-are tetrazotized, then coupled in alkaline solution on one side with 1.8 parts I of 1-hydroxybenzene-Z-sulfonic acid and then in neutral or weakly acid solution with 2.5- parts of 1-amino-2 1 a Member Selected oth the group consisting of a methoxynaphthalene-G-sulfonic acid. When the coupling benzene, naphthalene and blphenyleflefadlcal, 2 15 a is finished the disazo-dyestufr' obtained is isolated, then dimember from the group 60115150118 of b61116, azotized, and coupled in alkaline solution with 2.4 parts naphthalene blphenylenel of 2-amino-5-hydroxynaphthalene-7-sulfonic acid. The V trisazo-dyestuif is precipitated by the addition of sodium Q O chloride, then dissolved by the addition of 8 parts by volume of a 2 N-solution of sodium hydroxide, and di- Z and azotized after the addition of sodium nitrite and hydrochloric acid and a little ice in the usual manner. The

product is then coupled with 1.3 parts of barbituric acid in a solution rendered alkaline with sodium carbonate. The complex copper compound of the resulting dyestuif ('33,

of the formula s 0 H 0 OH;

O O-N is obtained by heating the dyestuif for several hours with and copper acetate in a weakly acetic acid solution. The copper compound is filtered off and dried, and is then a black OH powder which dissolves in concentrated sulfuric acid with (h-N- 3-GH=OH-O a blackish brown coloration and in water with a green coloration. It dyes vegetable fibers olive-green tints that are fast to light. 43

radical, and R is a member selected from the group con- '100 parts of cotton are entered at 40 C. into a dyesisting of a benzene, a biphenylene, a stilbene, a benzoylbath which contains in 3000 parts of water 1 part of the anilino, a dihydrothiotoluidine, an acetic acid anilide and dyestufi obtainable as described in the first paragraph of a naphthalene radical, and which dyestutf contains at least Example 1. Dyeing is carried on for half an hour while two sulfonic acid groups. raising the temperature of 90 C., then 30 parts of 2. Complex copper compounds of the polyazo-dyestuffs crystalline sodium sulfate are added, and dyeing is conof the formula Example 9 tinued for a further /2 hour at 90-95 C. The cotton is in which n=2, m=l and R represents a ipyrazolone then rinsed and dried. There is obtained a green dyeing radical which is bound in the 4-position to the of very good iastness to light. R N=N=group and in the l-positron through a What is claimed is: phenylene group to the -N=N.R =group R being 1. A complex copper compound of polyazo-dyestufis a naphthalene and R a benzene radical containing a sulof the formula ionic acid group.

3,078,268 1 '3' 1 8 3. Complex copper compounds of the polyazo-dyestuffs of the formula in which n is a whole number up to 2, R represents a benzene nucleus and R 21 l-phenyl S-pyrazolone radical bound to RN=N in 4 position and to the other azo l5 linkage through the phenyl substituent in its l-position.

4. The complex copper compound of the formula O O-NH SOaH 5. The complex copper compound of the formula 8. The complex copper compound of the formula 803B 5 CONH No references cited.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,0783% February 19 1963 Walter Hanhart It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column l line 541: for "aminonaphthlo" read aminonaphthol ;column 2 line ll for "cholro-anilines" read chloroanilines column 11,, line 63,, strike out "from"; columns 13 and ll at the bottom of the page extreme left-hand portion of theformula should appear as shown below instead of as in the patent:

SO3H

column 15, line 5 for "bartituric" read barbituric line 9, for "weekly" read weakly columns 17 and 18,

formula in claim 4 the extreme right-hand portion of the formula should appear as shown below instead of as in the patent:

same columns 17 and 18 the formula of claim 6 should appear as shown below instead of as in the patent:

S0311 CO-NH :N N=N N:N H038 H035 N:NCI-I\ /co 3 CONH s ma zaa same colur nns 17 and 18, the formula of claim 7 should appear as shown below instead of as in the patent:

CO-NH i HOGNSN 110 s CO-ON:N-CH c0 (IO-NH 80 1-1 same columns 17 and 18 the formula of claim-"8 sh-ou-l-d app as shownloelow instead of as in the patent:

so n

Signed and sealed this 24th day of December 1963,

(SEAL) Attest EDWIN L. REYNOLDS Acting Commissioner of Patents ERNEST W. SWIDER Attesting Officer 

1. A COMPLEX COPPER COMPOUND OF POLYAZO-DYESTUFFS OF THE FORMULA 